Redetermination of [Gd(NO3)3(H2O)4]·2H2O

Taha, Z.A.; Ajlouni, A.; Hijazi, A.K.; Kühn, F.E.; Herdtweck, E.

doi:10.1107/S1600536812028000

inorganic compounds

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ISSN: 2056-9890

Volume 68| Part 7| July 2012| Pages i56-i57

https://doi.org/10.1107/S1600536812028000

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Redetermination of [Gd(NO₃)₃(H₂O)₄]·2H₂O

Ziyad A. Taha,^a ^* Abdulaziz Ajlouni,^a Ahmed K. Hijazi,^b Fritz E. Kühn ^c and Eberhardt Herdtweck ^d ^*

^aDepartment of Applied Chemical Sciences, Jordan University of Science & Technology, Irbid 22110, Jordan, ^bDepartment of Chemistry, Faculty of Science, Jerash University, Jerash 26150, Jordan, ^cDepartment Chemie, Molekulare Katalyse, Technische Universität München, Lichtenbergstrasse 4, D-85747 Garching bei München, Germany, and ^dDepartment Chemie, Lehrstuhl für Anorganische Chemie, Technische Universität München, Lichtenbergstrasse 4, D-85747 Garching bei München, Germany
^*Correspondence e-mail: akh75_99@yahoo.com, eberhardt.herdtweck@ch.tum.de

(Received 18 May 2012; accepted 20 June 2012; online 27 June 2012)

The crystal structure of the title compound, tetraaquatris(nitrato-κ²O,O′)gadolinium(III) dihydrate, was redetermined from single-crystal X-ray data. In comparison with the first determination [Ma et al. (1991 ). Wuji Huaxue Xuebao, 7, 351–353], all H atoms could be located, accompanied with higher accuracy and precision. The Gd^III atom shows a ten-coordination with three nitrate ligands behaving in a bidentate manner and the other positions being occupied by four water molecules, forming a distorted bicapped square antiprism. Two nitrate ions coordinate to the metal atom with similar bond lengths while the third shows a more asymmetric bonding behaviour. An intricate network of O—H⋯O hydrogen bonds, including the lattice water molecules, stabilizes the crystal packing.

Related literature

For a previous determination of the title compound, see: Ma et al. (1991). Isotypic [RE(NO₃)₃(H₂O)₄]·2H₂O structures were described for RE = Nd by Rogers et al. (1983 ), for Tb by Moret et al. (1990 ), for Sm by Kawashima et al. (2000 ), for Eu by Stumpf & Bolte (2001 ), for Dy by Gao et al. (1990 ), and for La by Eriksson et al. (1980 ). [RE(NO₃)₃(H₂O)₄]·H₂O structures with one less water molecule were described for RE = Eu by Ribár et al. (1986 ), for Gd by Stockhause & Meyer (1997 ), and for Yb by Junk et al. (1999 ).

Experimental

Crystal data

[Gd(NO₃)₃(H₂O)₄]·2H₂O
M_r = 451.38
Triclinic, $[P \overline 1]$
a = 6.6996 (2) Å
b = 9.1145 (3) Å
c = 11.6207 (3) Å
α = 69.8257 (10)°
β = 88.9290 (11)°
γ = 69.2170 (11)°
V = 618.36 (3) Å³
Z = 2
Mo Kα radiation
μ = 5.45 mm⁻¹
T = 173 K
0.48 × 0.46 × 0.23 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.349, T_max = 0.745
19731 measured reflections
2256 independent reflections
2255 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.016
wR(F²) = 0.041
S = 1.20
2256 reflections
221 parameters
All H-atom parameters refined
Δρ_max = 1.04 e Å⁻³
Δρ_min = −1.10 e Å⁻³

Table 1
Selected bond lengths (Å)

Gd1—O1	2.528 (2)
Gd1—O2	2.494 (3)
Gd1—O4	2.578 (2)
Gd1—O5	2.518 (3)
Gd1—O7	2.552 (2)
Gd1—O8	2.754 (2)
Gd1—O10	2.398 (2)
Gd1—O11	2.389 (2)
Gd1—O12	2.392 (3)
Gd1—O13	2.364 (3)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O10—H1⋯O15ⁱ	0.76 (5)	1.97 (5)	2.720 (4)	171 (5)
O10—H2⋯O4ⁱⁱ	0.75 (4)	2.21 (4)	2.956 (3)	178 (6)
O11—H3⋯O14ⁱⁱⁱ	0.82 (4)	1.85 (4)	2.671 (3)	176 (5)
O11—H4⋯O7^iv	0.78 (5)	2.19 (5)	2.967 (4)	173 (5)
O12—H5⋯O4^v	0.77 (6)	2.50 (6)	3.185 (3)	149 (5)
O12—H5⋯O7^v	0.77 (6)	2.56 (6)	3.156 (4)	135 (5)
O12—H6⋯O8^vi	0.83 (5)	2.27 (5)	3.074 (3)	162 (4)
O12—H6⋯O9^vi	0.83 (5)	2.39 (5)	3.062 (4)	139 (4)
O13—H7⋯O15	0.90 (4)	1.84 (4)	2.721 (3)	169 (5)
O13—H8⋯O14	0.71 (4)	2.04 (4)	2.738 (4)	168 (5)
O14—H9⋯O9^iv	0.81 (5)	2.03 (5)	2.826 (4)	167 (4)
O14—H10⋯O3^v	0.76 (5)	2.45 (5)	3.008 (4)	132 (5)
O14—H10⋯O5^vii	0.76 (5)	2.31 (5)	2.888 (4)	134 (5)
O15—H11⋯O6ⁱⁱ	0.80 (6)	2.02 (6)	2.819 (4)	176 (6)
O15—H12⋯O3^viii	0.76 (6)	2.30 (6)	2.903 (4)	139 (5)
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x+2, -y+1, -z+1; (iii) -x+1, -y+1, -z; (iv) -x+2, -y+1, -z; (v) x-1, y, z; (vi) -x+1, -y+2, -z; (vii) x, y-1, z; (viii) -x+2, -y, -z+1.

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812028000/wm2634sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812028000/wm2634Isup2.hkl

checkCIF report

Comment top

Single crystals of gadolinium nitrate hexahydrate, [Gd(NO₃)₃(H₂O)₄]^.2H₂O, were obtained and its structure was re-determined using single-crystal X-ray diffraction analysis.

As shown in Figure 1, the Gd^III atom is ten-coordinated, being bound to six nitrate-oxygen atoms, O1, O2, O4, O5, O7, and O8, and four water-oxygen atoms O10, O11, O12, and O13. The nitrate ions are coordinated to the central gadolinium atom in a bidentate mode and show clearly the changes in bond lengths and angles noted previously for the isotypic Eu(III) structure (Stumpf & Bolte, 2001). The distances between the Gd^III ion and the nitrate-O atoms (Gd—O) are in the range 2.494 (3)–2.754 (2) Å, with a mean value of 2.571 Å. The differences between the Gd^III atom and the two oxygen atoms of the same nitrate group are 0.034 Å and 0.060 Å for nitrate N1 and nitrate N2, respectively. Nitrate N1 and nitrate N2 groups appear to be more symmetrically bonded to the Gd^III atom because the third nitrate group N3 exhibits one Gd—O distance that is 0.202 Å longer than the other. This asymmetric bonding seem to be associated with a steric effect of the coordinating water molecules. There is simply not space enough for all the oxygen atoms around the Gd^III atom at the same distance. The Gd—O_water distances are in the range of 2.364 (3)–2.398 (2) Å with an average distance of 2.386 Å. Hence the water molecules are closer to the Gd^III atom than the nitrate groups by ca. 0.185 Å.

These results are comparable to that reported for other lanthanide complexes with bidentately coordinating nitrate groups. The coordination polyhedron around the Gd^III ion can be best described as a distorted bi-capped square antiprism (Fig. 1), as previously reported for other hydrated lanthanide(III) nitrate complexes (Ribár et al., 1986; Moret et al., 1990; Ma et al., 1991, Stockhause & Meyer, 1997; Kawashima et al., 2000; Stumpf & Bolte, 2001; Junk et al., 1999; Gao et al., 1990; Eriksson et al., 1980; Rogers et al., 1983). The structure contains additional two lattice water molecules, which are associated with the complex by a network of hydrogen bonds. All hydrogen atoms and except for O1 and O2 all oxygen atoms are involved in a complicated network of O—H···O hydrogen bonds, stabilizing the crystal packing (Table 1, Fig. 2). H5, H6 and H10 act as bifurcated bridging atoms. In contrast to the original work of Ma et al. (1991), we report much more precise results. All hydrogen atoms could be located in the difference Fourier maps and were allowed to refine freely. The final R1 value changed from 0.076 to 0.0158 and the overall e.s.d.'s for the positional parameters dropped from e.g. Gd1 x = 0.8016 (1) to 0.80352 (2). The same is valid for distances e.g. Gd1—O1 dropped from 2.558 (56) Å to 2.528 (2) Å and for the angels e.g. O1—Gd1—O2 dropped from 51.1 (22) to 50.56 (7).

Related literature top

For a previous determination of the title compound, see: Ma et al. (1991). Isotypic [RE(NO₃)₃(H₂O)₄]^.2(H₂O) structures were described for RE = Nd by Rogers et al. (1983), for Tb by Moret et al. (1990), for Sm by Kawashima et al. (2000), for Eu by Stumpf & Bolte (2001), for Dy by Gao et al. (1990), and for La by Eriksson et al. (1980). [RE(NO₃)₃(H₂O)₄]^.(H₂O) structures with one less water molecule were described for RE = Eu by Ribár et al. (1986), for Gd by Stockhause & Meyer (1997), and for Yb by Junk et al. (1999).

Experimental top

Single crystals of [Gd(NO₃)₃(H₂O)₄]^.2H₂O have been obtained accidentally during the synthesis of a Gd—N,N-bis(salicylicaldehyde)-o-phenylenediamine Schiff base complex. 1.0 mmol of the Schiff base were dissolved in 10 ml chloroform. To this solution was added in a drop-wise manner a 10 ml ethyl acetate solution of 2.0 mmol Gd(NO₃)₃^.6(H₂O). The reaction mixture was stirred for 2 h at room temperature. The yellow precipitate was filtered, washed several times with ethyl acetate and chloroform. Single crystals suitable for X-ray were obtained after a few days by the slow evaporation of the solvent in an open atmosphere.

Structure description top

Single crystals of gadolinium nitrate hexahydrate, [Gd(NO₃)₃(H₂O)₄]^.2H₂O, were obtained and its structure was re-determined using single-crystal X-ray diffraction analysis.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. View of the title compound with the atom numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level.
	Fig. 2. Stereo plot of the expanded unit cell. Hydrogen bonds (dotted lines) are limited to a distance O···H of 2.35 Å.

Tetraaquatris(nitrato-κ²O,O')gadolinium(III) dihydrate top

Crystal data top

[Gd(NO₃)₃(H₂O)₄]·2H₂O	Z = 2
M_r = 451.38	F(000) = 434
Triclinic, P1	D_x = 2.424 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.6996 (2) Å	Cell parameters from 9802 reflections
b = 9.1145 (3) Å	θ = 1.9–25.4°
c = 11.6207 (3) Å	µ = 5.45 mm⁻¹
α = 69.8257 (10)°	T = 173 K
β = 88.9290 (11)°	Fragment, orange
γ = 69.2170 (11)°	0.48 × 0.46 × 0.23 mm
V = 618.36 (3) Å³

Data collection top

Bruker APEXII CCD diffractometer	2256 independent reflections
Radiation source: rotating anode FR591	2255 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
Detector resolution: 16 pixels mm^-1	θ_max = 25.4°, θ_min = 1.9°
phi– and ω–rotation scans	h = −8→8
Absorption correction: multi-scan (SADABS; Bruker, 2008)	k = −10→10
T_min = 0.349, T_max = 0.745	l = −13→13
19731 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.016	All H-atom parameters refined
wR(F²) = 0.041	Weighting scheme based on measured s.u.'s w = 1/[σ²(F_o²) + (0.0186P)² + 0.725P] where P = (F_o² + 2F_c²)/3
S = 1.20	(Δ/σ)_max = 0.001
2256 reflections	Δρ_max = 1.04 e Å⁻³
221 parameters	Δρ_min = −1.10 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0129 (7)

Crystal data top

[Gd(NO₃)₃(H₂O)₄]·2H₂O	γ = 69.2170 (11)°
M_r = 451.38	V = 618.36 (3) Å³
Triclinic, P1	Z = 2
a = 6.6996 (2) Å	Mo Kα radiation
b = 9.1145 (3) Å	µ = 5.45 mm⁻¹
c = 11.6207 (3) Å	T = 173 K
α = 69.8257 (10)°	0.48 × 0.46 × 0.23 mm
β = 88.9290 (11)°

Data collection top

Bruker APEXII CCD diffractometer	2256 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	2255 reflections with I > 2σ(I)
T_min = 0.349, T_max = 0.745	R_int = 0.036
19731 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.016	0 restraints
wR(F²) = 0.041	All H-atom parameters refined
S = 1.20	Δρ_max = 1.04 e Å⁻³
2256 reflections	Δρ_min = −1.10 e Å⁻³
221 parameters

Special details top

Experimental. Diffractometer operator E. Herdtweck scanspeed 10 s per frame dx 45 4932 frames measured in 9 data sets phi-scan with delta_phi = 0.50 omega-scans with delta_omega = 0.50

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except for 0 with very negative F² or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating R_factor_obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Gd1	0.80352 (2)	0.59425 (1)	0.22568 (1)	0.0147 (1)
O1	1.0817 (4)	0.3431 (3)	0.3878 (2)	0.0294 (7)
O2	1.1029 (4)	0.3531 (3)	0.20104 (19)	0.0286 (6)
O3	1.3338 (4)	0.1425 (3)	0.3490 (2)	0.0304 (6)
O4	1.0578 (3)	0.6801 (3)	0.3296 (2)	0.0268 (6)
O5	0.7353 (4)	0.8617 (3)	0.2653 (2)	0.0305 (7)
O6	0.9570 (4)	0.9177 (3)	0.3616 (2)	0.0319 (7)
O7	1.0495 (3)	0.6937 (3)	0.07347 (19)	0.0245 (6)
O8	0.7274 (4)	0.8794 (3)	0.0190 (2)	0.0336 (7)
O9	0.9806 (4)	0.9195 (3)	−0.0904 (2)	0.0322 (7)
O10	0.6976 (4)	0.5590 (3)	0.4287 (2)	0.0224 (7)
O11	0.7203 (4)	0.5521 (3)	0.04330 (19)	0.0223 (6)
O12	0.4279 (4)	0.7621 (3)	0.1754 (2)	0.0259 (7)
O13	0.6339 (4)	0.3963 (3)	0.2792 (2)	0.0262 (7)
N1	1.1767 (4)	0.2751 (3)	0.3141 (2)	0.0213 (7)
N2	0.9171 (4)	0.8234 (3)	0.3202 (2)	0.0233 (8)
N3	0.9183 (4)	0.8342 (3)	−0.0015 (2)	0.0212 (7)
O14	0.5912 (4)	0.2215 (3)	0.1372 (2)	0.0239 (7)
O15	0.6255 (4)	0.2025 (3)	0.5159 (2)	0.0258 (7)
H1	0.608 (7)	0.632 (6)	0.437 (4)	0.038 (12)*
H2	0.760 (6)	0.500 (5)	0.490 (4)	0.028 (11)*
H3	0.625 (6)	0.625 (5)	−0.011 (4)	0.025 (10)*
H4	0.789 (7)	0.491 (6)	0.012 (4)	0.037 (12)*
H5	0.341 (8)	0.724 (6)	0.193 (5)	0.056 (15)*
H6	0.369 (7)	0.865 (6)	0.135 (4)	0.046 (12)*
H7	0.649 (7)	0.328 (6)	0.358 (4)	0.043 (11)*
H8	0.640 (6)	0.344 (5)	0.245 (3)	0.019 (10)*
H9	0.705 (7)	0.183 (5)	0.113 (4)	0.035 (11)*
H10	0.561 (7)	0.151 (6)	0.181 (4)	0.048 (14)*
H11	0.741 (9)	0.167 (6)	0.554 (5)	0.053 (15)*
H12	0.589 (9)	0.131 (7)	0.522 (5)	0.069 (18)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Gd1	0.0156 (1)	0.0131 (1)	0.0141 (1)	−0.0049 (1)	0.0013 (1)	−0.0038 (1)
O1	0.0320 (12)	0.0258 (11)	0.0220 (11)	0.0000 (9)	−0.0012 (9)	−0.0096 (9)
O2	0.0307 (12)	0.0234 (11)	0.0190 (10)	0.0007 (9)	0.0036 (9)	−0.0040 (9)
O3	0.0254 (11)	0.0149 (10)	0.0366 (12)	0.0005 (9)	0.0011 (9)	−0.0006 (9)
O4	0.0246 (11)	0.0262 (11)	0.0298 (11)	−0.0082 (9)	0.0003 (9)	−0.0116 (9)
O5	0.0296 (12)	0.0181 (10)	0.0389 (13)	−0.0076 (9)	−0.0101 (10)	−0.0053 (9)
O6	0.0422 (14)	0.0241 (12)	0.0326 (12)	−0.0157 (11)	−0.0049 (10)	−0.0102 (10)
O7	0.0239 (11)	0.0200 (11)	0.0241 (10)	−0.0073 (9)	0.0020 (8)	−0.0024 (8)
O8	0.0213 (11)	0.0266 (12)	0.0495 (14)	−0.0051 (9)	0.0113 (10)	−0.0140 (11)
O9	0.0416 (13)	0.0205 (11)	0.0261 (11)	−0.0107 (10)	0.0118 (10)	0.0002 (9)
O10	0.0258 (12)	0.0208 (12)	0.0175 (11)	−0.0050 (10)	0.0025 (9)	−0.0072 (10)
O11	0.0260 (11)	0.0204 (11)	0.0162 (10)	−0.0040 (9)	−0.0005 (9)	−0.0061 (9)
O12	0.0182 (11)	0.0195 (12)	0.0354 (12)	−0.0055 (9)	−0.0007 (9)	−0.0058 (10)
O13	0.0445 (14)	0.0267 (12)	0.0178 (11)	−0.0233 (11)	0.0068 (9)	−0.0101 (10)
N1	0.0203 (12)	0.0136 (12)	0.0264 (13)	−0.0063 (10)	0.0027 (10)	−0.0029 (10)
N2	0.0305 (14)	0.0202 (13)	0.0182 (12)	−0.0125 (11)	−0.0018 (10)	−0.0023 (10)
N3	0.0247 (13)	0.0162 (12)	0.0222 (12)	−0.0070 (10)	0.0054 (10)	−0.0070 (10)
O14	0.0277 (12)	0.0189 (11)	0.0232 (11)	−0.0083 (10)	0.0008 (9)	−0.0057 (9)
O15	0.0328 (14)	0.0201 (12)	0.0245 (11)	−0.0118 (10)	0.0039 (10)	−0.0061 (9)

Geometric parameters (Å, º) top

Gd1—O1	2.528 (2)	O7—N3	1.277 (3)
Gd1—O2	2.494 (3)	O8—N3	1.243 (4)
Gd1—O4	2.578 (2)	O9—N3	1.227 (3)
Gd1—O5	2.518 (3)	O10—H1	0.76 (5)
Gd1—O7	2.552 (2)	O10—H2	0.75 (4)
Gd1—O8	2.754 (2)	O11—H3	0.82 (4)
Gd1—O10	2.398 (2)	O11—H4	0.78 (5)
Gd1—O11	2.389 (2)	O12—H5	0.77 (6)
Gd1—O12	2.392 (3)	O12—H6	0.83 (5)
Gd1—O13	2.364 (3)	O13—H7	0.90 (4)
O1—N1	1.260 (4)	O13—H8	0.71 (4)
O2—N1	1.268 (3)	O14—H9	0.81 (5)
O3—N1	1.228 (4)	O14—H10	0.76 (5)
O4—N2	1.280 (4)	O15—H11	0.80 (6)
O5—N2	1.259 (4)	O15—H12	0.76 (6)
O6—N2	1.223 (4)

O1—Gd1—O2	50.56 (7)	O8—Gd1—O12	68.70 (8)
O1—Gd1—O4	67.93 (8)	O8—Gd1—O13	130.50 (8)
O1—Gd1—O5	111.77 (8)	O10—Gd1—O11	140.10 (9)
O1—Gd1—O7	99.76 (8)	O10—Gd1—O12	79.72 (8)
O1—Gd1—O8	146.55 (9)	O10—Gd1—O13	71.04 (9)
O1—Gd1—O10	68.65 (9)	O11—Gd1—O12	78.30 (9)
O1—Gd1—O11	115.74 (9)	O11—Gd1—O13	71.47 (8)
O1—Gd1—O12	143.98 (8)	O12—Gd1—O13	75.61 (9)
O1—Gd1—O13	78.10 (9)	Gd1—O1—N1	95.96 (16)
O2—Gd1—O4	93.36 (8)	Gd1—O2—N1	97.41 (18)
O2—Gd1—O5	141.08 (9)	Gd1—O4—N2	95.25 (17)
O2—Gd1—O7	68.28 (8)	Gd1—O5—N2	98.75 (19)
O2—Gd1—O8	109.78 (8)	Gd1—O7—N3	101.83 (17)
O2—Gd1—O10	117.19 (8)	Gd1—O8—N3	92.94 (17)
O2—Gd1—O11	69.75 (8)	Gd1—O10—H2	129 (3)
O2—Gd1—O12	145.36 (9)	H1—O10—H2	110 (5)
O2—Gd1—O13	81.74 (9)	Gd1—O10—H1	118 (3)
O4—Gd1—O5	49.97 (8)	H3—O11—H4	105 (5)
O4—Gd1—O7	69.84 (7)	Gd1—O11—H3	122 (3)
O4—Gd1—O8	89.68 (8)	Gd1—O11—H4	131 (4)
O4—Gd1—O10	75.39 (8)	Gd1—O12—H6	128 (3)
O4—Gd1—O11	144.41 (8)	Gd1—O12—H5	122 (4)
O4—Gd1—O12	120.88 (9)	H5—O12—H6	109 (5)
O4—Gd1—O13	138.89 (7)	Gd1—O13—H8	122 (3)
O5—Gd1—O7	84.58 (8)	Gd1—O13—H7	120 (3)
O5—Gd1—O8	64.27 (7)	H7—O13—H8	104 (5)
O5—Gd1—O10	70.94 (8)	H9—O14—H10	110 (5)
O5—Gd1—O11	130.51 (8)	H11—O15—H12	110 (6)
O5—Gd1—O12	71.40 (9)	O1—N1—O2	116.1 (3)
O5—Gd1—O13	133.03 (9)	O1—N1—O3	122.2 (2)
O7—Gd1—O8	47.73 (8)	O2—N1—O3	121.7 (3)
O7—Gd1—O10	145.14 (8)	O4—N2—O5	116.0 (3)
O7—Gd1—O11	74.76 (8)	O4—N2—O6	122.0 (3)
O7—Gd1—O12	116.18 (8)	O5—N2—O6	122.0 (3)
O7—Gd1—O13	140.84 (8)	O8—N3—O9	122.0 (3)
O8—Gd1—O10	131.16 (8)	O7—N3—O8	117.5 (2)
O8—Gd1—O11	68.65 (8)	O7—N3—O9	120.5 (3)

O2—Gd1—O1—N1	−0.36 (17)	O11—Gd1—O5—N2	−134.37 (16)
O4—Gd1—O1—N1	−114.9 (2)	O12—Gd1—O5—N2	170.31 (18)
O5—Gd1—O1—N1	−139.49 (18)	O13—Gd1—O5—N2	122.60 (17)
O7—Gd1—O1—N1	−51.5 (2)	O1—Gd1—O7—N3	−171.29 (17)
O8—Gd1—O1—N1	−63.6 (3)	O2—Gd1—O7—N3	148.39 (19)
O10—Gd1—O1—N1	162.8 (2)	O4—Gd1—O7—N3	−109.28 (19)
O11—Gd1—O1—N1	26.2 (2)	O5—Gd1—O7—N3	−60.09 (18)
O12—Gd1—O1—N1	132.50 (19)	O8—Gd1—O7—N3	−0.29 (16)
O13—Gd1—O1—N1	88.7 (2)	O10—Gd1—O7—N3	−104.8 (2)
O1—Gd1—O2—N1	0.36 (17)	O11—Gd1—O7—N3	74.51 (18)
O4—Gd1—O2—N1	57.96 (19)	O12—Gd1—O7—N3	6.1 (2)
O5—Gd1—O2—N1	75.6 (2)	O13—Gd1—O7—N3	105.6 (2)
O7—Gd1—O2—N1	124.7 (2)	O1—Gd1—O8—N3	16.5 (3)
O8—Gd1—O2—N1	148.82 (18)	O2—Gd1—O8—N3	−30.59 (19)
O10—Gd1—O2—N1	−17.3 (2)	O4—Gd1—O8—N3	62.87 (18)
O11—Gd1—O2—N1	−154.2 (2)	O5—Gd1—O8—N3	107.53 (19)
O12—Gd1—O2—N1	−130.31 (19)	O7—Gd1—O8—N3	0.29 (16)
O13—Gd1—O2—N1	−80.99 (19)	O10—Gd1—O8—N3	132.99 (18)
O1—Gd1—O4—N2	−148.15 (17)	O11—Gd1—O8—N3	−88.21 (18)
O2—Gd1—O4—N2	167.14 (15)	O12—Gd1—O8—N3	−173.6 (2)
O5—Gd1—O4—N2	1.56 (14)	O13—Gd1—O8—N3	−126.70 (18)
O7—Gd1—O4—N2	101.75 (16)	Gd1—O1—N1—O2	0.6 (3)
O8—Gd1—O4—N2	57.34 (16)	Gd1—O1—N1—O3	179.5 (3)
O10—Gd1—O4—N2	−75.63 (16)	Gd1—O2—N1—O1	−0.6 (3)
O11—Gd1—O4—N2	108.04 (19)	Gd1—O2—N1—O3	−179.5 (3)
O12—Gd1—O4—N2	−7.40 (18)	Gd1—O4—N2—O5	−2.7 (2)
O13—Gd1—O4—N2	−111.58 (18)	Gd1—O4—N2—O6	177.6 (2)
O1—Gd1—O5—N2	28.63 (19)	Gd1—O5—N2—O4	2.7 (2)
O2—Gd1—O5—N2	−24.9 (2)	Gd1—O5—N2—O6	−177.5 (2)
O4—Gd1—O5—N2	−1.59 (14)	Gd1—O7—N3—O8	0.5 (3)
O7—Gd1—O5—N2	−69.73 (17)	Gd1—O7—N3—O9	−179.1 (2)
O8—Gd1—O5—N2	−114.96 (19)	Gd1—O8—N3—O7	−0.5 (3)
O10—Gd1—O5—N2	85.07 (17)	Gd1—O8—N3—O9	179.1 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O10—H1···O15ⁱ	0.76 (5)	1.97 (5)	2.720 (4)	171 (5)
O10—H2···O4ⁱⁱ	0.75 (4)	2.21 (4)	2.956 (3)	178 (6)
O11—H3···O14ⁱⁱⁱ	0.82 (4)	1.85 (4)	2.671 (3)	176 (5)
O11—H4···O7^iv	0.78 (5)	2.19 (5)	2.967 (4)	173 (5)
O12—H5···O4^v	0.77 (6)	2.50 (6)	3.185 (3)	149 (5)
O12—H5···O7^v	0.77 (6)	2.56 (6)	3.156 (4)	135 (5)
O12—H6···O8^vi	0.83 (5)	2.27 (5)	3.074 (3)	162 (4)
O12—H6···O9^vi	0.83 (5)	2.39 (5)	3.062 (4)	139 (4)
O13—H7···O15	0.90 (4)	1.84 (4)	2.721 (3)	169 (5)
O13—H8···O14	0.71 (4)	2.04 (4)	2.738 (4)	168 (5)
O14—H9···O9^iv	0.81 (5)	2.03 (5)	2.826 (4)	167 (4)
O14—H10···O3^v	0.76 (5)	2.45 (5)	3.008 (4)	132 (5)
O14—H10···O5^vii	0.76 (5)	2.31 (5)	2.888 (4)	134 (5)
O15—H11···O6ⁱⁱ	0.80 (6)	2.02 (6)	2.819 (4)	176 (6)
O15—H12···O3^viii	0.76 (6)	2.30 (6)	2.903 (4)	139 (5)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y+1, −z+1; (iii) −x+1, −y+1, −z; (iv) −x+2, −y+1, −z; (v) x−1, y, z; (vi) −x+1, −y+2, −z; (vii) x, y−1, z; (viii) −x+2, −y, −z+1.

Experimental details

Crystal data
Chemical formula	[Gd(NO₃)₃(H₂O)₄]·2H₂O
M_r	451.38
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	6.6996 (2), 9.1145 (3), 11.6207 (3)
α, β, γ (°)	69.8257 (10), 88.9290 (11), 69.2170 (11)
V (Å³)	618.36 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	5.45
Crystal size (mm)	0.48 × 0.46 × 0.23

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.349, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	19731, 2256, 2255
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.604

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.016, 0.041, 1.20
No. of reflections	2256
No. of parameters	221
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	1.04, −1.10

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Selected bond lengths (Å) top

Gd1—O1	2.528 (2)	Gd1—O8	2.754 (2)
Gd1—O2	2.494 (3)	Gd1—O10	2.398 (2)
Gd1—O4	2.578 (2)	Gd1—O11	2.389 (2)
Gd1—O5	2.518 (3)	Gd1—O12	2.392 (3)
Gd1—O7	2.552 (2)	Gd1—O13	2.364 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O10—H1···O15ⁱ	0.76 (5)	1.97 (5)	2.720 (4)	171 (5)
O10—H2···O4ⁱⁱ	0.75 (4)	2.21 (4)	2.956 (3)	178 (6)
O11—H3···O14ⁱⁱⁱ	0.82 (4)	1.85 (4)	2.671 (3)	176 (5)
O11—H4···O7^iv	0.78 (5)	2.19 (5)	2.967 (4)	173 (5)
O12—H5···O4^v	0.77 (6)	2.50 (6)	3.185 (3)	149 (5)
O12—H5···O7^v	0.77 (6)	2.56 (6)	3.156 (4)	135 (5)
O12—H6···O8^vi	0.83 (5)	2.27 (5)	3.074 (3)	162 (4)
O12—H6···O9^vi	0.83 (5)	2.39 (5)	3.062 (4)	139 (4)
O13—H7···O15	0.90 (4)	1.84 (4)	2.721 (3)	169 (5)
O13—H8···O14	0.71 (4)	2.04 (4)	2.738 (4)	168 (5)
O14—H9···O9^iv	0.81 (5)	2.03 (5)	2.826 (4)	167 (4)
O14—H10···O3^v	0.76 (5)	2.45 (5)	3.008 (4)	132 (5)
O14—H10···O5^vii	0.76 (5)	2.31 (5)	2.888 (4)	134 (5)
O15—H11···O6ⁱⁱ	0.80 (6)	2.02 (6)	2.819 (4)	176 (6)
O15—H12···O3^viii	0.76 (6)	2.30 (6)	2.903 (4)	139 (5)

Acknowledgements

The authors are grateful to the Deanship of Scientific Research at Jordan University of Science and Technology for the financial support of this work (grant No. 48/2008).

References

Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435. CrossRef Web of Science IUCr Journals Google Scholar
Bruker (2008). APEX, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Eriksson, B., Larsson, L. O., Niinisto, L. & Valkonen, J. (1980). Inorg. Chem. 19, 1207–1210. CrossRef CAS Web of Science Google Scholar
Gao, S., Ma, H. & Yang, Z. (1990). J. Northwest Univ. (China), 20, 53–58. CAS Google Scholar
Junk, P. C., Kepert, D. L., Skelton, B. W. & White, A. H. (1999). Aust. J. Chem. 52, 497–505. CAS Google Scholar
Kawashima, R., Sasaki, M., Satoh, S., Isoda, H., Kino, Y. & Shiozaki, Y. (2000). J. Phys. Soc. Jpn, 69, 3297–3303. Web of Science CrossRef CAS Google Scholar
Ma, H., Gao, S. & Zupci, Y. (1991). Wuji Huaxue Xuebao, 7, 351–353. CAS Google Scholar
Moret, E., Bünzli, J.-C. G. & Schenk, K. J. (1990). Inorg. Chim. Acta, 178, 83–88. CrossRef CAS Web of Science Google Scholar
Ribár, B., Kapor, A., Argay, Gy. & Kálmán, A. (1986). Acta Cryst. C42, 1450–1452. CrossRef Web of Science IUCr Journals Google Scholar
Rogers, D. J., Taylor, N. J. & Toogood, G. E. (1983). Acta Cryst. C39, 939–941. CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stockhause, S. & Meyer, G. (1997). Z. Kristallogr. New Cryst. Struct. 212, 315. Google Scholar
Stumpf, T. & Bolte, M. (2001). Acta Cryst. E57, i10–i11. Web of Science CrossRef IUCr Journals Google Scholar